Reductive release of Fe mineral-associated organic matter accelerated by oxalic acid.

The properties and composition of soil dissolved organic matter (DOM) are highly affected by the adsorption and desorption of organic matter (OM) on soil minerals and heterotrophic microbial respiration. Organic acids (e.g., oxalic acid), components of root exudates, have been revealed to liberate organic matter (OM) by the dissolution of protective mineral phases and stimulate microbial degradation of OM. However, the effects of organic acids on the properties and composition of soil DOM molecules and the related mechanisms are still poorly understood. In this study, we conducted microcosm incubation experiments with and without oxalic acid addition, and aimed to elucidate the variations of DOM properties and composition, employing a combination of Fourier transform ion cyclotron resonance mass spectrometry, optical spectroscopy, and bacterial community composition analysis. Our results indicated that the released OM from the direct dissolution of protective mineral phases by oxalic acid further stimulated the microbial reductive release of Fe mineral-associated OM under anoxic conditions. Furthermore, the addition of oxalic acid enhanced the degradation of aliphatic compounds and lignins with low O/C ratios, and increased the accumulation of lignins with high O/C ratios, tannins, and condensed aromatics. Linking the bacterial community composition to DOM molecular properties and composition further suggested that the enhanced reductive release of Fe mineral-associated OM was highly related to the increased abundances of Proteobacteria and Actinobacteria. Overall, oxalic acid induced long-lasting impacts on soil DOM properties and composition under anoxic soil conditions in our study. We expect that our results will contribute to understanding the dynamics of soil DOM molecules in the environment.

Chemodiversity of Soil Dissolved Organic Matter.

Dissolved organic matter (DOM) plays a key role in many biogeochemical processes, but the drivers controlling the diversity of chemical composition and properties of DOM molecules (chemodiversity) in soils are poorly understood. It has also been debated whether environmental conditions or intrinsic molecular properties control the accumulation and persistence of DOM due to the complexity of both molecular composition of DOM and interactions between DOM and surrounding environments. In this study, soil DOM samples were extracted from 33 soils collected from different regions of China, and we investigated the effects of climate and soil properties on the chemodiversity of DOM across different regions of China, employing a combination of Fourier transform ion cyclotron resonance mass spectrometry, optical spectroscopy, and statistical analyses. Our results indicated that, despite the heterogeneity of soil samples and complex influencing factors, aridity and clay can account for the majority of the variations of DOM chemical composition. The finding implied that DOM chemodiversity is an ecosystem property closely related to the environment, and can be used in developing large-scale soil biogeochemistry models for predicting C cycling in soils.

Binding characteristics of heavy metals to humic acid before and after fractionation by ferrihydrite.

The fractionation of humic substances (HS) at the mineral and water interface can change the constituents and reactivity of HS, but there is still a lack of the understanding of the effects of HS fractionation on the binding characteristics of heavy metals to HS. In this study, the binding characteristics of five heavy metals (Cd, Cu, Ni, Pb, and Zn) to humic acid (HA) before and after adsorption by ferrihydrite were investigated by employing two-dimensional correlation spectroscopy (2D COS) integrated with synchronous fluorescence and Fourier transform infrared (FTIR) spectroscopies. 2D COS analyses of the fluorescence results indicated that the susceptibility of the fluorescence of humic-like fraction to heavy metals significantly decreased after the adsorption of HA by ferrihydrite, which may be due to the fact that humic-like components were preferentially adsorbed by ferrihydrite. However, the fractionation processes did not alter the metal binding sequence and affinity to different HA components. 2D COS analyses of the FTIR results suggested that fractionation processes decreased the susceptibility of COO- groups to heavy metals, and changed the metal binding sequence to polysaccharides C-O and aryl groups, with the exception of Pb. Furthermore, model calculations showed that the binding ability of heavy metals to both humic-like and fulvic-like fractions decreased after the adsorption of HA by ferrihydrite. The results of this study contribute to predicting heavy metal behavior in the environment.

Modeling kinetics of Ni dissociation from humic substances based on WHAM 7.

Understanding the kinetics of Ni dissociation from dissolved organic matter (DOM) helps to better predict the fate and bioavailability of Ni ions in the environment. However, there is still a lack of predictive models for the kinetics of Ni dissociation from DOM under different reaction conditions. In this study, kinetics of Ni dissociation from humic acids (HA) and fulvic acids (FA), two most important components in DOM for Ni binding, was studied with a competing ligand exchange method at varying Ni concentrations, reaction pH, and ionic strength. The kinetic data were analyzed using a mechanistic kinetics model developed based on the Windermere Humic Aqueous Model (WHAM). Experimental results showed that Ni dissociation rates were affected by both Ni concentrations and pH, and Ni dissociation from FA had faster rates than that from HA. The kinetics model can reproduce the experimental data well, with only two model fitting parameters for different reaction conditions. The modeling results showed that various HA and FA binding sites played different roles in controlling Ni dissociation rates, with bidentate binding sites and the weak tridentate sites being the most significant. At high pH values the Ni re-association reactions were significant for controlling the overall rates of Ni dissociation but had minimal impact at lower pH values. Our model provided a modeling framework based on WHAM 7 for predicting Ni dissociation rates when humic substances were the dominant binding ligands.